Catalyst system and its use in a polymerization process

ABSTRACT

The present invention relates to a catalyst system of a Group 15 containing metal catalyst compound and a Lewis acid aluminum containing activator and to a supported catalyst system thereof and to a process for polymerizing olefin(s) utilizing them.

[0001] Furthermore, U.S. Pat. No. 5,576,460 describes a preparation ofarylamine ligands and U.S. Pat. No. 5,889,128 discloses a process forthe living polymerization of olefins using initiators having a metalatom and a ligand having two group 15 atoms and a group 16 atom or threegroup 15 atoms. EP 893 454 A1 also describes preferably titaniumtransition metal amide compounds. In addition, U.S. Pat. No. 5,318,935discusses amido transition metal compounds and catalyst systemsespecially for the producing isotactic polypropylene. Polymerizationcatalysts containing bidentate and tridentate ligands are furtherdiscussed in U.S. Pat. No. 5,506,184.

[0002] While all these compounds have been described in the art, thereis still a need for an improved catalyst system.

SUMMARY OF THE INVENTION

[0003] This invention provides for a catalyst system and for its use inpolymerizing process.

[0004] In one embodiment, the invention is directed to a catalyst systemof a Group 15 containing transition metal catalyst compound and a Lewisacid activator and to its use in the polymerization of olefin(s).

[0005] In another embodiment, the invention is directed to a catalystsystem of a Group 15 containing bidentate or tridentate ligatedtransition metal catalyst compound and a Lewis acid aluminum containingactivator to its use in the polymerization of olefin(s).

[0006] In another embodiment, the invention is directed to a catalystsystem having a transition metal bound to at least one leaving group andalso bound to at least two Group 15 atoms, at least one of which is alsobound to a Group 15 or 16 atom through another group, and a Lewis acidaluminum containing activator, and to its use in the polymerization ofolefin(s).

[0007] In still another embodiment, the invention is directed to amethod for supporting the multidentate metal based catalyst system, andto the supported catalyst system itself.

[0008] In another embodiment, the invention is directed to a process forpolymerizing olefin(s), particularly in a gas phase or slurry phaseprocess, utilizing any one of the catalyst systems or supported catalystsystems discussed above.

DETAILED DESCRIPTION OF THE INVENTION

[0009] Introduction

[0010] It has been found that catalyst systems of a Group 15 containingtransition metal catalyst compound and a Lewis acid aluminum containingactivators exhibit commercially acceptable productivity with excellentoperability. Also, in particular the catalyst system of the invention issupportable on a support material, preferably for use in a slurry or gasphase polymerization process.

[0011] Group 15 Containing Metal Catalyst Compound and Catalyst Systems

[0012] In one embodiment, the metal based catalyst compounds of theinvention are Group 15 bidentate or tridentate ligated transition metalcompound having at least one substituted hydrocarbon group, thepreferred Group 15 elements are nitrogen and/or phosphorous, mostpreferably nitrogen, and the preferred leaving group is a substitutedalkyl group having greater than 6 carbon atoms, preferably the alkylsubstituted with an aryl group.

[0013] The Group 15 containing metal catalyst compounds of the inventiongenerally include a transition metal atom bound to at least onesubstituted hydrocarbon leaving group and also bound to at least twoGroup 15 atoms, at least one of which is also bound to a Group 15 or 16atom through another group.

[0014] In one preferred embodiment, at least one of the Group 15 atomsis also bound to a Group 15 or 16 atom through another group, which maybe a hydrocarbon group, preferably a hydrocarbon group having 1 to 20carbon atoms, a heteroatom containing group, preferably silicon,germanium, tin, lead, or phosphorus. In this embodiment, it is furtherpreferred that the Group 15 or 16 atom be bound to nothing or ahydrogen, a Group 14 atom containing group, a halogen, or a heteroatomcontaining group. Additionally in these embodiment, it is preferred thateach of the two Group 15 atoms are also bound to a cyclic group that mayoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

[0015] In an embodiment of the invention, the Group 15 containing metalcompound of the invention is represented by the formulae:

[0016] wherein M is a metal, preferably a transition metal, morepreferably a Group 4,5 or 6 metal, even more preferably a Group 4 metal,and most preferably hafnium or zirconium; each X is independently aleaving group, preferably, an anionic leaving group, and more preferablyhydrogen, a hydrocarbyl group, a heteroatom, and most preferably analkyl. In a most preferred embodiment, at least one X is a substitutedhydrocarbon group, preferably a substituted alkyl group having more than6 carbon atoms, more preferably an aryl substituted alkyl group and mostpreferably a benzyl group.

[0017] y is 0 or 1 (when y is 0 group L′ is absent);

[0018] n is the oxidation state of M, preferably +2, +3, +4 or +5 andmore preferably +4;

[0019] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2;

[0020] L is a Group 15 or 16 element, preferably nitrogen;

[0021] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium;

[0022] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen;

[0023] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen;

[0024] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, arylor arylalkyl group, more preferably a linear, branched or cyclic C₂ toC₂₀ alkyl group, most preferably a C₂ to C₆ hydrocarbon group;

[0025] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen; R⁴ and R⁵ areindependently an alkyl group, an aryl group, substituted aryl group, acyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkylgroup, a substituted cyclic arylalkyl group or multiple ring system,preferably having up to 20 carbon atoms, more preferably between 3 and10 carbon atoms, and even more preferably a C₁ to C₂₀ hydrocarbon group,a C₁ to C₂₀ aryl group or a C₁ to C₂₀ arylalkyl group, or a heteroatomcontaining group, for example PR₃, where R is an alkyl group;

[0026] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other;

[0027] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent; and

[0028] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

[0029] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0030] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and RS may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0031] An alkyl group may be a linear, branched alkyl radicals, oralkenyl radicals, alkynyl radicals, cycloalkyl radicals or arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An arylalkyl group is defined to be a substitutedaryl group.

[0032] In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

[0033] wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀alkyl group, a halide, a heteroatom, a heteroatom containing groupcontaining up to 40 carbon atoms, preferably a C₁ to C₂₀ linear orbranched alkyl group, preferably a methyl, ethyl, propyl or butyl group,any two R groups may form a cyclic group and/or a heterocyclic group.The cyclic groups may be aromatic. In a preferred embodiment R⁹, R¹⁰ andR¹² are independently a methyl, ethyl, propyl or butyl group (includingall isomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methylgroups, and R⁸ and R¹¹ are hydrogen.

[0034] In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

[0035] In this embodiment, M is hafnium or zirconium; each of L, Y, andZ is nitrogen; each of R¹ and R² is a hydrocarbyl group, preferably—CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷ are absent.

[0036] The Group 15 containing metal catalyst compounds of the inventionare prepared by methods known in the art, such as those disclosed in EP0 893 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S.Pat. No. 5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference. A preferred directsynthesis of these compounds comprises reacting the neutral ligand, (seefor example YZL or YZL′ of Formula I or II) with MX_(n), n is theoxidation state of the metal, each X is an anionic group, such ashalide, in a non-coordinating or weakly coordinating solvent, such asether, toluene, xylene, benzene, methylene chloride, and/or hexane orother solvent having a boiling point above 60° C., at about 20° C. toabout 150° C. (preferably 20° C. to 100° C.), preferably for 24 hours ormore, then treating the mixture with an excess (such as four or moreequivalents) of an alkylating agent, such as methyl magnesium bromide inether. The magnesium salts are removed by filtration, and the metalcomplex isolated by standard techniques.

[0037] In one embodiment the Group 15 containing metal catalyst compoundis prepared by a method comprising reacting a neutral ligand, (see forexample YZL or YZL′ of formula 1 or 2) with a compound represented bythe formula MX, (where n is the oxidation state of M, M is a transitionmetal, and each X is an anionic leaving group) in a non-coordinating orweakly coordinating solvent, at about 20° C. or above, preferably atabout 20° C. to about 100° C., then treating the mixture with an excessof an alkylating agent, then recovering the metal complex. In apreferred embodiment the solvent has a boiling point above 60° C., suchas toluene, xylene, benzene, and/or hexane. In another embodiment thesolvent comprises ether and/or methylene chloride, either beingpreferable.

[0038] Activator and Activation Methods

[0039] The above described Group 15 containing metal catalyst compoundsare typically activated in various ways to yield catalyst compoundshaving a vacant coordination site that will coordinate, insert, andpolymerize olefin(s).

[0040] The preferred activator is a Lewis acid compound, more preferablyan aluminum based Lewis acid compound, and most preferably a neutral,aluminum based Lewis acid compound having at least one, preferably two,halogenated aryl ligands and one or two additional monoanionic ligandsnot including halogenated aryl ligands.

[0041] The Lewis acid compounds of the invention include those olefincatalyst activator Lewis acids based on aluminum and having at least onebulky, electron-withdrawing ancillary ligand such as the halogenatedaryl ligands of tris(perfluorophenyl)borane ortris(perfluoronaphthyl)borane. These bulky ancillary ligands are thosesufficient to allow the Lewis acids to function as electronicallystabilizing, compatible non-coordinating anions. Stable ionic complexesare achieved when the anions will not be a suitable ligand donor to thestrongly Lewis acidic cationic Group 15 containing transition metalcations used in insertion polymerization, i.e., inhibit ligand transferthat would neutralize the cations and render them inactive forpolymerization.

[0042] The Lewis acids fitting this description can be described by thefollowing formula:

R_(n)Al(ArHal)_(3-n),  (V)

[0043] where R is a monoanionic ligand and ArHal is a halogenated C₆aromatic or higher carbon number polycyclic aromatic hydrocarbon oraromatic ring assembly in which two or more rings (or fused ringsystems) are joined directly to one another or together, and n=1 to 2,preferably n=1.

[0044] In one embodiment, at least one (ArHal) is a halogenated Cgaromatic or higher, preferably a fluorinated naphtyl. Suitablenon-limiting R ligands include: substituted or unsubstituted C₁ to C₃₀hydrocarbyl aliphatic or aromatic groups, substituted meaning that atleast one hydrogen on a carbon atom is replaced with a hydrocarbyl,halide, halocarbyl, hydrocarbyl or halocarbyl substitutedorganometalloid, dialkylamido, alkoxy, siloxy, aryloxy, alkysulfido,arylsulfido, alkylphosphido, alkylphosphido or other anionicsubstituent; fluoride; bulky alkoxides, where bulky refers to C₄ andhigher number hydrocarbyl groups, e.g., up to about C₂₀, such astert-butoxide and 2,6-dimethyl-phenoxide, and2,6-di(tert-butyl)phenoxide; —SR; —NR₂, and —PR₂, where each R isindependently a substituted or unsubstituted hydrocarbyl as definedabove; and, C₁ to C₃₀ hydrocarbyl substituted organometalloid, such astrimethylsilyl.

[0045] Examples of ArHal include the phenyl, napthyl and anthracenylradicals of U.S. Pat. No. 5,198,401 and the biphenyl radicals of WO97/29845 when halogenated. The use of the terms halogenated orhalogenation means for the purposes of this application that at leastone third of hydrogen atoms on carbon atoms of the aryl-substitutedaromatic ligands are replaced by halogen atoms, and more preferred thatthe aromatic ligands be perhalogenated. Fluorine is the most preferredhalogen.

[0046] Other activators or methods of activation are contemplated foruse with the aluminum based Lewis acid activators. For example otheractivators include: alumoxane, modified alumoxane, tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions, trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate,perchlorates, periodates, iodates and hydrates,(2,2′-bisphenyl-ditrimethylsilicate)•4THF and organo-boron-aluminumcompound, silylium salts anddioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)-benzimidazolide.

[0047] It is further contemplated by the invention that other catalystsincluding bulky ligand metallocene-type catalyst compounds and/orconventional-type catalyst compounds can be combined with the Group 15containing metal catalyst compounds of this invention.

[0048] Supports, Carriers and General Supporting Techniques

[0049] The above described catalyst systems of a Group 15 containingmetal catalyst compound and a Lewis acid aluminum containing activatormay be combined with one or more support materials or carriers using oneof the support methods well known in the art or as described below. Forexample, in a most preferred embodiment, a Group 15 containing metalcatalyst compound and Lewis acid activator is in a supported form, forexample deposited on, contacted with, vaporized with, bonded to, orincorporated within, adsorbed or absorbed in, or on, a support orcarrier.

[0050] The R group in formula (V) above, or ligand, may also be acovalently bonded to a support material, preferably a metal/metalloidoxide or polymeric support. Lewis base-containing support materials orsubstrates will react with the Lewis acid activators to form a supportbonded Lewis acid compound, a supported activator, where one R group ofR_(n)Al(ArHal)₃, is covalently bonded to the support material. Forexample, where the support material is silica, the Lewis base hydroxylgroups of the silica is where this method of bonding at one of thealuminum coordination sites occurs.

[0051] In a preferred embodiment, the support material is a metal ormetalloid oxide, preferably having surface hydroxyl groups exhibiting apK_(a) equal to or less than that observed for amorphous silica, i.e.,pK_(a) less than or equal to about 11.

[0052] While not wishing to be bound to any particular theory, it isbelieved that the covalently bound anionic activator, the Lewis acid, isbelieved to form initially a dative complex with a silanol group, forexample of silica (which acts as a Lewis base), thus forming a formallydipolar (zwitterionic) Bronsted acid structure bound to themetal/metalloid of the metal oxide support. Thereafter, the proton ofthe Bronsted acid appears to protonate an R′-group of the Lewis acid,abstracting it, at which time the Lewis acid becomes covalently bondedto the oxygen atom. The replacement R group of the Lewis acid thenbecomes R′—O—, where R′ is a suitable support material or substrate, forexample, silica or hydroxyl group-containing polymeric support. Anysupport material that contain surface hydroxyl groups are suitable foruse in this particular supporting method. Other support material includeglass beads.

[0053] In one embodiment where the support material is a metal oxidecomposition, these compositions may additionally contain oxides of othermetals, such as those of Al, K, Mg, Na, Si, Ti and Zr and shouldpreferably be treated by thermal and/or chemical means to remove waterand free oxygen. Typically such treatment is in a vacuum in a heatedoven, in a heated fluidized bed or with dehydrating agents such asorgano silanes, siloxanes, alkyl aluminum compounds, etc. The level oftreatment should be such that as much retained moisture and oxygen as ispossible is removed, but that a chemically significant amount ofhydroxyl functionality is retained. Thus calcining at up to 800° C. ormore up to a point prior to decomposition of the support material, forseveral hours is permissible, and if higher loading of supported anionicactivator is desired, lower calcining temperatures for lesser times willbe suitable. Where the metal oxide is silica, loadings to achieve fromless than 0.1 mmol to 3.0 mmol activator/g SiO₂ are typically suitableand can be achieved, for example, by varying the temperature ofcalcining from 200 to 800+° C. See Zhuralev, et al, Langmuir 1987, Vol.3, 316 where correlation between calcining temperature and times andhydroxyl contents of silica's of varying surface areas is described.

[0054] The tailoring of hydroxyl groups available as attachment sitescan also be accomplished by the pre-treatment, prior to addition of theLewis acid, with a less than stoichiometric amount of the chemicaldehydrating agents. Preferably those used will be used sparingly andwill be those having a single ligand reactive with the silanol groups(e.g., (CH₃)₃SiCl), or otherwise hydrolyzable, so as to minimizeinterference with the reaction of the transition metal catalystcompounds with the bound activator. If calcining temperatures below 400°C. are employed, difunctional coupling agents (e.g., (CH₃)₂SiCl₂) may beemployed to cap hydrogen bonded pairs of silanol groups which arepresent under the less severe calcining conditions. See for example,“Investigation of Quantitative SiOH Determination by the SilaneTreatment of Disperse Silica”, Gorski, et al, Journ. of Colloid andInterface Science, Vol. 126, No. 2, Dec. 1988, for discussion of theeffect of silane coupling agents for silica polymeric fillers that willalso be effective for modification of silanol groups on the catalystsupports of this invention. Similarly, use of the Lewis acid in excessof the stoichiometric amount needed for reaction with the transitionmetal compounds will serve to neutralize excess silanol groups withoutsignificant detrimental effect for catalyst preparation or subsequentpolymerization.

[0055] Polymeric supports are preferablyhydroxyl-functional-group-containing polymeric substrates, butfunctional groups may be any of the primary alkyl amines, secondaryalkyl amines, and others, where the groups are structurally incorporatedin a polymeric chain and capable of a acid-base reaction with the Lewisacid such that a ligand filling one coordination site of the aluminum isprotonated and replaced by the polymer incorporated functionality. See,for example, the functional group containing polymers of U.S. Pat. No.5,288,677, which is herein incorporated by reference.

[0056] Other supports include silica, alumina, silica-alumina, magnesia,titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate,zeolites, talc, clays, silica-chromium, silica-alumina, silica-titania,porous acrylic polymers.

[0057] In one embodiment, the support material or carrier, mostpreferably an inorganic oxide has a surface area in the range of fromabout 10 to about 100 m²/g, pore volume in the range of from about 0.1to about 4.0 cc/g and average particle size in the range of from about 5to about 500 μm. More preferably, the surface area of the carrier is inthe range of from about 50 to about 500 m²/g, pore volume of from about0.5 to about 3.5 cc/g and average particle size of from about 10 toabout 200 μm. Most preferably the surface area of the carrier is in therange is from about 100 to about 400 m²/g, pore volume from about 0.8 toabout 5.0 cc/g and average particle size is from about 5 to about 100μm. The average pore size of the carrier of the invention typically haspore size in the range of from 10 to 1000 Å, preferably 50 to about 500Å, and most preferably 75 to about 450 Å.

[0058] There are various other methods in the art for supporting apolymerization catalyst compound or catalyst system of the invention.

[0059] In a preferred embodiment, the invention provides for a Group 15containing metal catalyst system includes a surface modifier that isused in the preparation of the supported catalyst system as described inPCT publication WO 96/11960, which is herein fully incorporated byreference. The catalyst systems of the invention can be prepared in thepresence of an olefin, for example hexene-1.

[0060] In a preferred embodiment, the Group 15 containing metal catalystsystem can be combined with a carboxylic acid salt of a metal ester, forexample aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

[0061] A preferred method for producing a supported Group 15 containingmetal catalyst system is described below and is described in U.S.application Ser. Nos. 265,533, filed Jun. 24, 1994 and Ser. No. 265,532,filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO 96/00243both published Jan. 4, 1996, all of which are herein fully incorporatedby reference. In this preferred method, the Group 15 containing metalcatalyst compound is slurried in a liquid to form a solution and aseparate solution is formed containing a Lewis acid activator and aliquid. The liquid may be any compatible solvent or other liquid capableof forming a solution or the like with the Group 15 containing metalcatalyst compounds and/or Lewis acid activator. In the most preferredembodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon,most preferably toluene. The Group 15 containing metal catalystcompounds and Lewis acid activator solutions are mixed together andadded to a porous support such that the total volume of Group 15containing metal catalyst compound solution and the Lewis acid activatorsolution or the Group 15 containing metal catalyst compound solution andLewis acid activator solution is less than four times the pore volume ofthe porous support, more preferably less than three times, even morepreferably less than two times; preferred ranges being from 1.1 times to3.5 times range and most preferably in the 1.2 to 3 times range.

[0062] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0063] The mole ratio of the metal of the activator component to themetal component of the Group 15 containing metal catalyst compound ispreferably in the range of between 0.3:1 to 3:1.

[0064] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the catalystsystem of the invention prior to the main polymerization. Theprepolymerization can be carried out batchwise or continuously in gas,solution or slurry phase including at elevated pressures. Theprepolymerization can take place with any olefin monomer or combinationand/or in the presence of any molecular weight controlling agent such ashydrogen. For examples of prepolymerization procedures, see U.S. Pat.Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578and European publication EP-B-0279 863 and PCT Publication WO 97/44371all of which are herein fully incorporated by reference.

[0065] Polymerization Process

[0066] The catalyst systems, supported catalyst systems or compositionsof the invention described above are suitable for use in anyprepolymerization and/or polymerization process over a wide range oftemperatures and pressures. The temperatures may be in the range of from−60° C. to about 280° C., preferably from 50° C. to about 200° C., andthe pressures employed may be in the range from 1 atmosphere to about500 atmospheres or higher.

[0067] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0068] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0069] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0070] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0071] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0072] In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms.

[0073] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0074] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0075] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0076] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0077] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0078] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0079] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0080] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0081] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, whichare fully incorporated herein by reference

[0082] A process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of the catalystsystem of the invention and in the absence of or essentially free of anyscavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. Nos. 5,712,352 and 5,763,543,which are herein fully incorporated by reference.

[0083] In an embodiment, the method of the invention provides forinjecting an unsupported metal catalyst system of the invention into areactor, particularly a gas phase reactor. In one embodiment thecatalyst system is used in the unsupported form, preferably in a liquidform such as described in U.S. Pat. Nos. 5,317,036 and 5,693,727 andEuropean publication EP-A-0 593 083, all of which are hereinincorporated by reference. The polymerization catalyst in liquid formcan be fed with an activator together or separately to a reactor usingthe injection methods described in PCT publication WO 97/46599, which isfully incorporated herein by reference. Where an unsupported catalystsystem is used the mole ratio of the metal of the Lewis acid activatorcomponent to the metal of the Group 15 containing metal catalystcompound is in the range of between 0.3:1 to 10,000: 1, preferably 100:1to 5000: 1, and most preferably 500:1 to 2000:1.

[0084] Polymer Products

[0085] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

[0086] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

[0087] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 15, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

[0088] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0089] The polymers of the invention in one embodiment have CDBI'sgenerally in the range of greater than 50% to 100%, preferably 99%,preferably in the range of 55% to 85%, and more preferably 60% to 80%,even more preferably greater than 60%, still even more preferablygreater than 65%.

[0090] In another embodiment, polymers produced using a catalyst systemof the invention have a CDBI less than 50%, more preferably less than40%, and most preferably less than 30%.

[0091] The polymers of the present invention in one embodiment have amelt index (MI) or (12) as measured by ASTM-D-1238-E in the range fromno measurable flow to 1000 dg/min, more preferably from about 0.01dg/min to about 100 dg/min, even more preferably from about 0.1 dg/minto about 50 dg/min, and most preferably from about 0.1 dg/min to about10 dg/min.

[0092] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) ( I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0093] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0094] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117, all of which are herein incorporated byreference.

[0095] The Group 15 containing metal compound, when used alone, producesa high weight average molecular weight M_(w) polymer (such as forexample above 100,000, preferably above 150,000, preferably above200,000, preferably above 250,000, more preferably above 300,000).

[0096] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, polypropylenes andthe like.

[0097] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

EXAMPLES

[0098] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0099] Synthesis of Al(C₆F₅)₃•toluene was prepared in accordance withmethod of described in EP 0 694 548 A1, which is fully incorporated byreference.

Example 1

[0100] Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH Ligand (HN3)

[0101] A 2 L one-armed Schlenk flask was charged with a magnetic stirbar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51g, 0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemicBINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol),and toluene (800 mL) under dry, oxygen-free nitrogen. The reactionmixture was stirred and heated to 100 C. After 18 h the reaction wascomplete, as judged by proton NMR spectroscopy. All remainingmanipulations can be performed in air. All solvent was removed undervacuum and the residues dissolved in diethyl ether (1 L). The ether waswashed with water (three times with 250 mL) followed by saturatedaqueous NaCl (180 g in 500 mL) and dried over magnesium sulfate (30 g).Removal of the ether in vacuo yielded a red oil which was dried at 70 Cfor 12 h under vacuum (yield: 71.10 g, 92%). ¹H NMR (C₆D₆) δ 6.83 (s,4), 3.39 (br s, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6),0.68 (br s, 1).

Example 2

[0102] Preparation of {[(2,4 6-Me₃C₆H₂ NCH₂CH₂]₂NH}Zr(CH₂Ph)₂ (Zr—HN₃)

[0103] A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific, Mead, Colo.) (41.729 g, 91.56mmol), and 300 mL of toluene under dry, oxygen-free nitrogen. Solid HN3ligand above (32.773 g, 96.52 mmol) was added with stirring over 1minute (the desired compound precipitates). The volume of the slurry wasreduced to 100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield). ¹H NMR (C₆D₆) 67 7.22-6.81 (m, 12), 5.90 (d, 2),3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41(s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

Example 3

[0104] Preparation of {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Hf(CH₂Ph)₂ (Hf—HN3)

[0105] A 250 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl hafnium (4.063 g, 7.482 mmol), and 150 mL of toluene underdry, oxygen-free nitrogen. Solid triamine ligand above (2.545 g, 7.495mmol) was added with stirring over 1 minute (the desired compoundprecipitates). The volume of the slurry was reduced to 30 mL and 120 mLof pentane added with stirring. The solid pale yellow product wascollected by filtration and dried under vacuum (4.562 g, 87% yield). ¹HNMR (C₆D₆) 67 7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14 (m, 2),2.65 (s, 6), 2.40 (s, 6), 2.35 (m, 2), 2.23 (m, 2), 2.19 (s, 6) 1.60 (s,2), 1.26 (s, 2), NH obscured.

Example 4

[0106] Preparation of Silica Bound Aluminum (Si—O—Al(C₆E₅)₂)

[0107] A sample of 40.686 g of silica (Davison 948, calcined at 600C,available from W.R. Grace, Davison Division, Baltimore, Md.) wasslurried in 300 mL of toluene in a 500 mL round bottom flask. SolidAl(C₆F₅)₃•toluene (15.470 g, 24.90 mmol) was added and the mixturestirred for 30 minutes. The mixture was allowed to stand for 18 hours.The silica bound aluminum was isolated by filtration and dried for 6hours under vacuum with a yield of 49.211 g.

Example 5

[0108] Preparation of Catalyst A

[0109] To 1.000 g of silica bound aluminum (from Example 4 above) in 20mL of toluene was added Zr—HN3 (0.076 g, 0.124 mmol) in 5 mL of toluene.The mixture was stirred for 30 minutes. The silica turned orange-redfrom colorless. The silica was isolated by filtration and dried undervacuum for 6 hours with a yield of 1.051 g. The final transition metalloading was 116 μmol/g, transition metal to silica bound aluminum.

Example 6

[0110] Preparation of Catalyst B

[0111] To 1.000 g of silica bound aluminum (from Example 4 above) in 20mL of toluene was added Hf—HN3 (0.087 g, 0.125 mmol) in 5 mL of toluene.The mixture was stirred for 30 minutes. The silica turned orange-redfrom colorless. The silica was isolated by filtration and dried undervacuum for 6 hours with a yield of 1.059 g. The final transition metalloading was 115 μmol/g, transition metal to silica bound aluminum.

Example 7

[0112] Slurry-Phase Ethylene-Hexene Polymerization with Catalyst A

[0113] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet and vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Isobutane (400 mL) is added as a diluent, 35 mL of1-hexene, and 0.7 mL of a 25 weight percent trioctyl aluminum in hexaneis added as a scavenger using a gas tight syringe. The reactor washeated to 60° C. 0.100 g of finished Catalyst A was added with ethylenepressure and the reactor was pressurized with 78 psi (538 kPa) ofethylene. The polymerization was continued for 30 minutes whilemaintaining the reactor at 60° C. and 78 psi (538 kPa) by constantethylene flow. The reaction was stopped by rapid cooling and vented.70.0 g of copolymer was obtained (Flow Index (FI)=no flow, activity=2320g polyethylene/mmol catalyst•atm•h, 10.5 weight percent 1-hexeneincorporation).

Example 8

[0114] Slurry-Phase Ethylene Polymerization with Catalyst B

[0115] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet and vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Isobutane (400 mL) was added as a diluent and 0.7 mLof a 25 weight percent trioctyl aluminum solution in hexane was added asa scavenger using a gas tight syringe. The reactor was heated to 90° C.0.200 g of finished Catalyst B was added with ethylene pressure and thereactor was pressurized with 134 psi (924 kPa) of ethylene. Thepolymerization was continued for 30 minutes while maintaining thereactor at 90° C. and 134 psi (924 kPa) by constant ethylene flow. Thereaction was stopped by rapid cooling and vented. 37.4 g of polyethylenewas obtained (FI=no flow, activity=364 g polyethylene/mmolcatalyst•atm•rh).

Example 9

[0116] Slurry-Phase Ethylene-Hexene Polymerization with Catalyst B

[0117] Polymerization was performed in the slurry-phase in a 1-literautoclave reactor equipped with a mechanical stirrer, an external waterjacket for temperature control, a septum inlet and vent line, and aregulated supply of dry nitrogen and ethylene. The reactor was dried anddegassed at 160° C. Isobutane (400 mL) is added as a diluent, 35 mL of1-hexene, and 0.7 mL of a 25 weight percent trioctyl aluminum in hexaneis added as a scavenger using a gas tight syringe. The reactor washeated to 90° C. 0.100 g of finished catalyst B was added with ethylenepressure and the reactor was pressurized with 113 psi (889 kPa) ofethylene. The polymerization was continued for 25 minutes whilemaintaining the reactor at 90° C. and 113 psi (889 kPa) by constantethylene flow. The reaction was stopped by rapid cooling and vented.68.0 g of polyethylene was obtained (FI=no flow, activity=1650 gpolyethylene/mmol catalyst•atm•h).

[0118] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that twoor more supported Group 15 containing catalyst compositions of theinvention can be used in a single or in multiple polymerization reactorconfigurations. For this reason, then, reference should be made solelyto the appended claims for purposes of determining the true scope of thepresent invention.

We claim:
 1. A process for polymerizing olefin(s) in the presence of acatalyst system comprising a Group 15 containing metal catalyst compoundand a Lewis acid aluminum containing activator.
 2. The process of claim1 wherein the Group 15 containing metal catalyst compound is a Group 15containing bidentate or tridentate ligated metal catalyst compound. 3.The process of claim 1 wherein the Group 15 containing metal catalystcompound is a metal atom bound to at least one substituted alkyl leavinggroup having 6 or greater carbon atoms and to at least two Group 15atoms, where at least one of the at least two Group 15 atoms is bound toa Group 15 or 16 atom through a bridging group.
 4. The process of claim3 wherein the bridging group is selected from the group consisting of aC₁ to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, and phosphorus.
 5. The process of claim 4 whereinthe Group 15 or 16 atom may also be bound to nothing, a hydrogen, aGroup 14 atom containing group, a halogen, or a heteroatom containinggroup, and wherein each of the two Group 15 atoms are also bound to acyclic group and may optionally be bound to hydrogen, a halogen, aheteroatom or a hydrocarbyl group, or a heteroatom containing group. 6.The process of claim 1 wherein the Group 15 containing metal compound isrepresented by the formulae:

wherein M is metal; each X is a leaving group; y is 0 or 1; n is theoxidation state of M; m is the formal charge of the YZL or the YZL′ligand; L is a Group 15 or 16 element; L′ is a Group 15 or 16 element orGroup 14 containing group; Y is a Group 15 element; Z is a Group 15element; R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus; R³ is absent or a hydrocarbongroup, hydrogen, a halogen, a heteroatom containing group; R⁴ and R⁵ areindependently an alkyl group, an aryl group, substituted aryl group, acyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkylgroup, a substituted cyclic arylalkyl group or multiple ring system; R¹and R² may be interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other; R⁶ and R⁷ are independently absent, orhydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group;and R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.
 7. The process of claim 6wherein R⁴ and R⁵ are represented by the formula:

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms, preferably a C₁ to C₂₀ linear or branched alkylgroup, preferably a methyl, ethyl, propyl or butyl group, any two Rgroups may form a cyclic group and/or a heterocyclic group. The cyclicgroups may be aromatic.
 8. The process of claim 7 wherein R⁹, R¹⁰ andR¹² are independently a methyl, ethyl, propyl or butyl group and X is asubstituted alkyl group having greater than 6 carbon atoms.
 9. Theprocess of claim 7 wherein R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ andR¹¹ are hydrogen and X is a alkyl substituted with an aryl group. 10.The process of claim 6 wherein L, Y, and Z are independently nitrogen,R¹ and R² are a hydrocarbon radical, R³ is hydrogen, and R⁶ and R⁷ areabsent.
 11. The process of claim 6 wherein L and Z are independentlynitrogen, L′ is a hydrocarbyl radical, and R⁶ and R⁷ are absent.
 12. Theprocess of claim 1 wherein the catalyst system is supported on acarrier.
 13. The process of claim 1 wherein the process is a continuousgas phase process.
 14. The process of claim 1 wherein the process is acontinuous slurry phase process.
 15. The process of claim 1 wherein theolefin(s) is ethylene or propylene.
 16. The process of claim 1 whereinthe olefins are ethylene and at least one other monomer having from 3 to20 carbon atoms.
 17. The process of claim 1 wherein the catalysts systemfurther comprises an activator.
 18. A supported catalyst systemcomprising: a Group 15 containing metal catalyst compound, an activatorand a carrier.
 19. The supported catalyst system of claim 18 wherein theGroup 15 containing metal catalyst compound is a Group 15 containingbidentate or tridentate ligated metal catalyst compound having asubstituted hydrocarbon leaving group.
 20. The supported catalyst systemof claim 18 wherein the Group 15 containing metal catalyst compound iscontacted with the activator to form a reaction product that is thencontacted with the carrier.